CN102334563A - Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil - Google Patents
Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil Download PDFInfo
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- CN102334563A CN102334563A CN201010228009XA CN201010228009A CN102334563A CN 102334563 A CN102334563 A CN 102334563A CN 201010228009X A CN201010228009X A CN 201010228009XA CN 201010228009 A CN201010228009 A CN 201010228009A CN 102334563 A CN102334563 A CN 102334563A
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
- C11B3/02—Refining fats or fatty oils by chemical reaction
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
- C11B3/00—Refining fats or fatty oils
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Abstract
The invention discloses a method for effectively controlling the content of 3-mono-chloropropane-1, 2-diol- or 3-mono-chloropropane-1, 2-diol or 3-mono- chloropropane- 1, 2-diol esters (3-MCPD or 3-MCPD FE) generated in an oil refining process. The method is characterized by comprising the following steps of: (A) degumming; (B) alkali refining: adding an alkali solution in the oil phase obtained in the step (A) to neutralize the oil phase obtained in the step (A); (C) soap removal: adding hot water into the oil phase obtained in the step (B) to remove soapstock; (D) decolorizing an oil phase obtained in the step (A); (E) enabling the decolorized oil obtained in the step of (D) to contact with water, wherein a step (E1) of mixing with water and a step (E2) of exchanging with ester are included in the step; (F) separating a water phase and drying the oil phase obtained in the step (E); and (G) introducing nitrogen gas or steam to the oil phase obtained in the step (F) to deodorize. The invention also relates to a method for controlling the content of 3-chloro-1,2-propanediol or ester thereof in an oil refining process and a method for controlling the content of 3-chloro-1,2-propanediol or ester thereof formed by oil in the deodorizing step. The invention aims to controlling the content of 3-chloro-1,2-propanediol or ester thereof in an oil refining process to be at lower level to ensure the safety of foods. The method provided by the invention is simple and feasible, and is easy for realizing industrialization and lower in production cost.
Description
Technical field
The present invention relates to the processing method of edible oil and fat, specifically, the present invention relates to is a kind of edible oil and fat processing method of improvement, promptly in the process of polished fat, controls 3-chloro-1, the method for 2-propane diols or its ester (3-MCPD/3-MCPD FE) content.
Background technology
Crude oil refer generally to from leach or squeezing process by the grease of some impurity that contains inedibility (or industrial) that extracts plant or the animal.
The main component of crude oil is the mixture (being commonly called as neutral oil) of fatty acid triglyceride.Except that neutral oil, also contain nonglyceride material (general designation impurity) in the crude oil, its kind, character, state are broadly divided into three major types such as mechanical admixture, oil-soluble impurities and water-solubility impurity.
Oil and fat refining typically refers to crude oil is made with extra care.The existence of impurity in the crude oil not only influences the edibility and the safe storage of grease, and brings difficulty to deep processing; But the purpose of refining; Non-again impurity all in the oil is all removed, but will wherein be removed, all remove like gossypol, protein, phosphatide, mucus, moisture etc. to impurity pernicious such as edible, storage, commercial production; And useful " impurity " will keep like tocopherol etc.Therefore, according to different requirement and purposes, unwanted and harmful impurity being removed from grease, obtained meeting the product oil of certain mass standard, is exactly the purpose of oil and fat refining.
3-chloro-1,2-propane diols (3-MCPD) is internationally recognized carcinogenic contaminant, it mainly results among the processed process of food.The refining process of grease also can increase 3-chloro-1, the content of 2-propane diols greatly.3-chloro-1 in grease, 2-propane diols mainly exist with two kinds of forms: alcohol and ester, and major part is an ester.In addition, the 3-chloro-1 that different oil are planted, the 2-content of propylene glycol also is not quite similar, and the Chemical &Veterinary Test Agency (CVUA) of Germany is to the 3-chloro-1 of frequently seen plants grease, and the 2-content of propylene glycol roughly is divided into following three intervals:
1. low content (0.5-1.5ppm): soybean oil, rapeseed oil, sunflower oil, coconut wet goods;
2. middle content (1.5-4ppm): peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive wet goods;
High-load (＞4ppm): hydrogenated oil and fat, solid frying oil, palm wet goods;
Wherein, the refining palm oil comes to light and contains 4-30mg/Kg, is the highest during all oil are planted.
Human body 3-every day chloro-1 in European Union's regulation food in 2002, the highest intake of 2-propane diols (TDI) is 2 μ g/Kg (human body body weight).This German Bundesinstitut f ü r Risikobewertung (BfR) is supposed 3-chloro-1; 2-propane diols-ester is become free 3-chloro-1 by lipase 100% hydrolysis in human body; The 2-propane diols; This will be considerably beyond safety standard, such as baby milk powder be TDI 12.5-20 doubly, the vegetable fat that the adult eats be TDI 5-10 doubly.
In sum, be necessary the refinery practice of grease is improved to avoid occurring safety issue.People such as K.Franke have delivered " Influence of chemical refining process and oil type on bound 3-chloro-1 in 2009; 2-propanediol contents in palm oil and rapeseed oil "; Main comparative chemistry purifying method is to the hair palm oil in this piece document; 3-chloro-1 in refining palm oil and the hair rape oil, the influence of 2-propane diols.The palmitic 3-chloro-1 of the double refining that experimental result obtains, 2-content of propylene glycol are about 4.56ppm, and the initial refining palm oil is about 4.39ppm, and rape oil is about 1.04ppm, and its content is still higher.
The research that decolouring and the temperature of deodorization procedures and time are carried out shows that deodorization is a 3-chloro-1, and the 2-propane diols mainly forms the stage, and preceding 20 minutes is the main time period.As everyone knows, the deodorizing technology of grease generally will maintain 45-90 minute, not so can't optimize the gas flavour of polished fat, indexs such as color and luster and acid value.Further research shows that monoglyceride and sweet diester in the grease possibly be 3-chloro-1, the precursor substance of 2-propane diols.Certainly will reach through some means with high costs or that can not carry out suitability for industrialized production such as enzyme reaction or molecular clock but reduce the two content in grease, this has little significance for actual production.
Therefore, this area presses for 3-chloro-1 in a kind of new reduction polished fat, 2-propane diols and 3-chloro-1, the method for 2-propane diols-ester of providing.
Summary of the invention
The present invention aims to provide a kind of plant produced cost and can effectively be controlled at 3-chloro-1 in polished fat's process of excessively not increasing, the 2-propane diols with and the method for ester content, method of the present invention is applicable to food industrialization production, can realize industrial-scale production; A further object of the present invention provides optimized process and the polished fat of the high-quality that obtained by this optimization technology.
The objective of the invention is to realize through following design:
A kind of 3-chloro-1 of in the process of polished fat, controlling, the method for 2-propane diols or its ester content, the process of described polished fat comprise (D) decolouring step; (G) deodorization step
It is characterized in that described method comprises:
In the preceding step of coming unstuck of described decolouring step (D) (A),
Have (B) alkali refining step between the described step of coming unstuck (A) and described (D) the decolouring step and (C) remove the soap step, described alkali refining step (B) comprises in the oil phase of step (A) gained and adds aqueous slkali, with the oil phase of neutralization procedure (A) gained; The described soap step (C) of removing comprises that adding hot water is to remove soap stock in the oil phase of step (B) gained; And
Between described decolouring step (D) and deodorization step (F), carry out the following step: (E) bleached oil is carried out the step that contacts with water, this step comprises mixes (E1) with water; And/or (E2) step of transesterification; (F) water phase separated, the drying steps (E1) or (E2) oil phase of gained;
In a preferred embodiment; Described step of transesterification (E2) comprising: the bleached oil of step (D) gained is warming up to 90 ℃-120 ℃; Add the catalyst that accounts for said bleached oil weight 0.1-2wt%; Described catalyst is a sodium methoxide, and catalyst can also be 1.NaOH, 2. alkali metal (1 and 2 is shared with glycerine usually); Perhaps, described step of transesterification (E2) comprising: the bleached oil of step (D) gained is warming up to 40 ℃-60 ℃, adds the ester exchange enzyme that accounts for said bleached oil weight 0.1-2wt% and under vacuum, react after 30 minutes cessation reaction;
The described step of coming unstuck comprises crude oil, the methods such as medium and water mixing of coming unstuck; The described medium that comes unstuck is selected from citric acid solution, phosphoric acid solution, and degummase uses degummase, and reaction system is generally at the 50-80 degree, PH-5-6, and the time is at 2-4h.May use citric acid (NaOH) buffer solution suitably to regulate pH value during commercial production) to 5-6; The described medium that comes unstuck is the 0.05wt% that is not less than crude oil weight, and the water yield is not less than the 0.5%wt of crude oil weight; The described medium that comes unstuck is in the gross weight of solution, and wherein the concentration of acid is not less than 5wt%.
In routine techniques, the available natural clay that is selected from of decolouring step (D), atlapulgite, active carbon, decoloring medium such as attapulgite are carried out; The preferably sulfuric acid treated earth.
In preferred embodiments, described decolouring step (D) comprising:
(i) under the vacuum oil phase of step (C) gained is warming up to 80-90 ℃;
(ii) add the sulfuric acid treated earth;
(iii) be warming up to 100-110 ℃ again, keep vacuum stirring to be not less than 10 minutes; With
(iv) filter to remove described sulfuric acid treated earth;
In the said step (E), the consumption of said water is more than or equal to the heavy 0.5wt% of the bleached oil of step (D) gained; Said be blended in not to be higher than under 95 ℃ carry out.
The present invention also provides a kind of control grease in the deodorization step, to form 3-chloro-1; The method of 2-propane diols or its ester comprises: before the deodorization step, make the refined oil of decolouring carry out water-washing step (E); During comprising, this step adds the step (E1) that water mixes, and/or step of transesterification (E2); And water phase separated, the step of the oil phase of dry gained (F).
Described bleached oil can obtain available from the refining techniques in market or through routine.
In optimized technical scheme, after described method also is included in the deodorization step, make the refined oil of decolouring carry out the step (E) that contacts with water again, this step comprises and adds the step (E1) that water mixes, and/or step of transesterification (E2); And, the step of the step (F) of the moisture oil phase of dry gained.
The present invention also provides a kind of method of polished fat, it is characterized in that, described method comprises the following steps:
(A) acidifying water wash-out glue step;
(A-1) oil phase of drying steps (A) gained;
(D) to the processing of decolouring of the oil phase of step (A-1) gained;
(E1) bleached oil and the water with step (D) gained mixes; And/or
(E2) step of transesterification
(F) water phase separated, drying steps (E1) and/or (E2) resulting oil phase; With
(G) oil phase to step (F) gained feeds nitrogen or steam, makes its deodorization.
Described oil and fat refining method preferably also comprises in step (A) with (D): (B) alkali refining step: the oil phase that adds aqueous slkali neutralization procedure (A-1) gained; (C) remove the soap step: in the oil phase of step (B) gained, add hot water to remove soap stock; (C-1) water phase separated, drying steps: the oil phase that step (C) is obtained carries out drying.
Described step of transesterification (E2) and the described step and above-mentioned described identical of coming unstuck.The described medium that comes unstuck is the 0.05wt% that is not less than crude oil weight, and the water yield is not less than the 0.5wt% of crude oil weight; The described medium that comes unstuck is in the gross weight of solution, and wherein the concentration of acid is not less than 5wt%.Described decolouring step (D) comprising:
(i) under the vacuum oil phase of step (C-1) gained is warming up to 80-90 ℃;
(ii) add the sulfuric acid treated earth;
(iii) be warming up to 100-110 ℃ again, keep vacuum stirring to be not less than 10 minutes; With
(iv) filter to remove described sulfuric acid treated earth.
In the said step (E), the consumption of said water is more than or equal to the heavy 0.5wt% of the bleached oil of step (D) gained; Said be blended in not to be higher than under 95 ℃ carry out.
Used crude oil or described bleached oil come since the grease that leaches or squeezing process extracts in by vegetable oil material or animal among the present invention; Comprise; But be not limited to soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat, palm wet goods vegetable fat and animal fat or its mixture.
With the refined oil that the inventive method obtains, in the gross weight of said refined oil, wherein the 3-chloro-1, and the content of 2-propane diols and/or its ester is smaller or equal to 0.5ppm.
In one embodiment; Between described decolouring step (D) and deodorization step (G), carry out the following step: (E) bleached oil is carried out the step that contacts with water; Described step (E) refers to mix with water the step (E1) of washing, or mixes with moisture material (like ethanolic solution) and to wash, or carries out a chemistry or physical process; Contain the step that bleached oil is contacted with water in this process, like the step of transesterification of (E2).
The specific embodiment
The inventor is surprised to find that if in the process of polished fat through extensive and deep research, particularly before the deodorization step, makes oil phase moisture; Water phase separated then; Dry oil phase carries out deodorization again and handles, and just helps reducing the content of 3-MCPD in the refined oil or 3-MCPD FE.
The inventor also finds, through improving the step of coming unstuck in polished fat's technical process, can reduce the content of 3-MCPD in the refined oil or 3-MCPD FE effectively.Specifically, the described step of coming unstuck is an acidifying water wash-out glue step, and it can reduce content of material such as phosphatide effectively, and and then further reduces the content of 3-MCPD in the refined oil or 3-MCPD FE.
In the refinery practice of the grease of prior art, alkali refining step (or neutralization procedure) and to remove the soap step be optional step.But the inventor finds, described alkali refining step and follow-up is removed the precursor substance that phosphorus and 3-MCPD or 3-MCPD FE can further fall in the soap step, like the chlorion equal size, thereby further reduces the content of 3-MCPD in the refined oil or 3-MCPD FE.
Particularly; The invention provides a kind of control grease and in the deodorization step, form 3-chloro-1; The method of 2-propane diols or its ester comprises: before the deodorization step, carry out (a) washing: bleached oil be not higher than 95 ℃ down and account for the said pure water that is not less than the 0.5wt% of bleached oil weight and mix; Wash, centrifugation subsequently obtains grease; (b) drying: (b) drying: stirred 5-30 minute after oil phase is warming up to 80-110 ℃, obtain washing oil, during need to keep vacuum.
The inventor also finds, controls the content of phosphorus containg substances (like phosphatide) in the refined oil process effectively, helps reducing the content of 3-MCPD in the refined oil or 3-MCPD FE.Especially, before deodorization was handled, phosphorus containg substances was low more in the grease, helps the reduction of the content of 3-MCPD or 3-MCPD FE more.
Bleached oil described in the said method is in its gross weight; Wherein phosphorus content (PHOS) is smaller or equal to 5ppm, preferably smaller or equal to 3ppm, during more preferably smaller or equal to 1ppm; The content of 3-MCPD or 3-MCPD FE can be reduced to low-down level, below 0.5ppm.
Described bleached oil be from leach or squeezing process by extract the plant and animal, through the grease of refining decolouring; Comprise; But be not limited to soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat, palm wet goods vegetable fat and animal fat or its mixture.
Preferably, in the said method step (a) to step (b) is carried out 1,2 or repeatedly.
Can after step (b), comprise step (c) in the above-mentioned method that provides: feed nitrogen or water vapour and serve as the deodorization medium; Vacuum is not higher than 25mBarA; Under suitable temperature deodorization 45-90 minute, can abolish vacuum below 50 ℃, cross and filter refined oil through deodorization.
The present invention also provides a kind of preparation method of refined oil, comprises step:
(A) acidifying water wash-out glue: under 80-90 ℃,, stir to centrifugalize after 30-40 minute and get oil phase 1 with crude oil, come unstuck medium and pure water mixing;
(A-1) drying: stirred 5-30 minute after oil phase 1 is warming up to 80-110 ℃, during need to keep vacuum;
(D) decolouring: add decolorizer after keeping vacuum to be warming up to 80-90 ℃, be warming up to 100-110 ℃ subsequently, keep vacuum stirring to be not less than 10 minutes, filter subsequently, obtain bleached oil to remove decolorizer;
(E) washing: bleached oil adding under 70-95 ℃ is not less than the heavy pure water of 0.5wt% oil and washes, and oil phase 2 is got in centrifugation subsequently; With
(F) drying: stirred 5-30 minute after oil phase 2 is warming up to 80-110 ℃, during need to keep vacuum;
(G) deodorization: feed nitrogen or water vapour and serve as the deodorization medium, vacuum is not higher than 25mBarA, and under suitable temperature deodorization 45-90 minute, can abolish vacuum below 50 ℃, cross and filter refined oil through deodorization.
The bleached oil that step (D) obtains is in its gross weight, and wherein phosphorus content (PHOS) is smaller or equal to 5ppm, preferably smaller or equal to 3ppm, more preferably smaller or equal to 1ppm.
Preferably, in the said method step (A) is repeated 2 or 3 times.
Preferably, in the said method step (A) to step (G) is repeated 2 or 3 times.
In a preference of the present invention, the preparation method of refined oil provided by the invention comprises step:
(1) acidifying water wash-out glue: under 80-90 ℃,, stir to centrifugalize after 30-40 minute and get oil phase 1 with crude oil, come unstuck medium and pure water mixing;
(2) drying: stirred 20-30 minute after oil phase 1 is warming up to 80-110 ℃, during need to keep vacuum;
(3) alkali refining (neutralization): under 80-90 ℃, add appropriate alkaline liquor and 1 reaction of dried oil phase;
(4) remove soap: add an amount of hot water down to remove soap stock at 80-90 ℃;
(5) drying: stirred after gently being warming up to 90 ℃ mutually 30 minutes, during keep vacuum
(6) decolouring: add decolorizer after keeping vacuum to be warming up to 80-90 ℃, be warming up to 100-110 ℃ subsequently, keep vacuum stirring to be not less than 10 minutes, filter subsequently, obtain bleached oil to remove decolorizer;
(7) washing: bleached oil adding under 70-95 ℃ is not less than the heavy pure water of 0.5wt% oil and washes, and oil phase 2 is got in centrifugation subsequently;
(8) drying: stirred 5-30 minute after oil phase 2 is warming up to 80-110 ℃, during need to keep vacuum, obtain refined oil;
(9) deodorization: feed nitrogen or water vapour and serve as the deodorization medium, vacuum is not higher than 25mBarA, and under suitable temperature deodorization 45-90 minute, can abolish vacuum below 50 ℃, cross and filter refined oil through deodorization.
The bleached oil that step (6) obtains is in its gross weight, and wherein phosphorus content (PHOS) is smaller or equal to 5ppm, preferably smaller or equal to 3ppm, more preferably smaller or equal to 1ppm.
Preferably, step (1) is carried out 2 or 3 times.
Preferably, step (1) to (9) is carried out 2 or 3 times.
Alkali lye described in the step (3) can be any alkaline solution, preferably is selected from sodium hydroxide solution, potassium hydroxide solution.Said concentration of lye is not for being higher than 35%wt.Used hot water is the hot water more than 50 ℃ in the step (4).
In the preparation method of refined oil provided by the invention, in acidifying water wash-out glue step, the described medium that comes unstuck is selected from citric acid solution, the described medium that comes unstuck in the gross weight of solution, and wherein the concentration of acid is for being not less than 5wt%.
In the preparation method of refined oil provided by the invention, in acidifying water wash-out glue step, the said medium that comes unstuck is not less than the 0.05wt% of crude oil weight, and water is not less than the 0.5wt% of crude oil weight.
In the preparation method of refined oil provided by the invention, in the decolouring step, described decolouring can be that the conventional method in this area is carried out, and described decolorizer includes but not limited to, natural clay, atlapulgite, active carbon, attapulgite etc.; The preferably sulfuric acid treated earth.
In the preparation method of refined oil provided by the invention, preferably, after deodorization step (9), the deodorization oil phase of gained is washed again, it is not moisture to guarantee in the final refined oil to carry out drying afterwards; Be described step washing, water phase separated, dry oil phase step is as step of the present invention (7) and (8).
In the preparation method of refined oil provided by the invention, can insert the step that adds ester exchange (containing washing)+drying in any operation stage.The step of described ester exchange+drying can be the conventional method in this area, such as but not limited to, with grease and sodium methoxide mix, with citric acid cessation reaction, washing mixture to neutral, the centrifugal oil phase that obtains, in vacuum intensification drying.
As used herein; " crude oil " is meant and comes since the grease that leaches or squeezing process extracts in by plant and animal; Comprise; But be not limited to soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat, palm wet goods vegetable fat and animal fat; In the gross weight of crude oil, wherein the content of 3-MCPD is more than the 0.5ppm.The preferred free fatty acid content of the present invention is not higher than the hair palm oil of 3wt%.
As used herein, " refined oil " is meant in its gross weight, and wherein the content of 3-MCPD is not for being higher than the grease of 1ppm.
With the refined oil that the inventive method obtains, in its gross weight, wherein the 3-chloro-1, and the content of 2-propane diols and/or its ester is smaller or equal to 0.5ppm.
Major advantage of the present invention is:
1,3-chloro-1 in the resulting refined oil of the preparation method of refined oil provided by the invention, the 2-propane diols with and ester content can be below 0.5ppm.
2, refined oil provided by the invention has greatly been alleviated the grease safety issue.
3, refined oil preparation method low production cost provided by the invention, and be very easy to realize commercial productionization.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in the restriction scope of the present invention.The experimental technique of unreceipted actual conditions in the following example is usually according to the normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or umber by weight.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example is meant the weight of solute in 100 milliliters solution.
Only if definition separately, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any with the institute similar content of putting down in writing or the equalization method and material all can be applicable in the inventive method.The usefulness that preferable implementation method described in the literary composition and material only present a demonstration.
In following examples, 3-MCPD Determination on content method is: the indirect method of measurement.Behind certain pretreatment procedure, detect acquisition through gas chromatography (GC-MS).
Test Example 1:
The relation of 3-MCPD content in content of phospholipid and the polished fat
The crude oil quality is seen table 1
The conventional physical and chemical index of table 1 mao palm oil (about 3%FFA)
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film, high purity lecithin (purity＞95%)
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.1% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. decolouring: under 110 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
4. raising content of phospholipid: under 70 ℃, bleached oil is added a certain amount of refined lecithin, at the uniform velocity stirred 1 hour;
5. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and quality are as shown in the table:
| The sample name | Phosphorus content | 3-MCPD content |
| Bleached oil | 1.07 | 0.67 |
| Bleached oil behind the interpolation lecithin | 36.68 | 0.69 |
| Deodorised oil | 20.17 | 7.38 |
3-MCPD content has certain correlation in Test Example proof content of phospholipid and the polished fat.
Embodiment 1:
Dry degumming (not having washing, drying)-contrast
The crude oil quality is seen table 1
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. dry degumming: use the heavy citric acid solution (50% concentration) of 0.1% oil, kept vacuum stirring 15 minutes down at 90 ℃, subsequently the light phase of centrifuging and taking;
2. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
3. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are following:
This embodiment shows that the bleached oil of using conventional dry degumming to obtain can obviously increase the formation of 3-MCPD after the deodorization step,
Embodiment 2
Acidifying water wash-out glue+physical refining
The crude oil quality is referring to the table 1 shown in the Test Example 1:
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.1% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. decolouring: under 110 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
4. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are as shown in the table:
This embodiment shows, adopts acidifying water wash-out glue step can reduce the formation of 3-MCPD in the deodorization step.
Embodiment 3
Dry degumming+washing bleached oil
The crude oil quality is seen the table 1 shown in the Test Example 1
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by reverse osmosis membrane
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. dry degumming: use the heavy citric acid solution (50% concentration) of 0.1% oil, kept vacuum stirring 15 minutes down at 90 ℃, subsequently the light phase of centrifuging and taking;
2. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
3. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
4. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
5. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are following:
This embodiment shows, only with the washing drying steps, but adopts conventional dry degumming, can not reduce the content of the 3-MCPD that forms in the deodorization step effectively.
Embodiment 4
Acidifying water wash-out glue+washing bleached oil
The crude oil quality is seen the table 1 shown in the Test Example 1
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.1% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. decolouring: under 110 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
4. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
5. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
6. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are following:
This embodiment shows, adopts acidifying water wash-out glue and washing and drying bleached oil can effectively control the formation of 3-MCPD in the deodorization step.
Embodiment 5
Double refining (repeatedly refining)
Adopt Test Example 1 employed crude oil;
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation);
Technological process is following:
Getting 1200g hair palm oil operates as follows:
1. dry degumming: the hair palm oil is used the heavy citric acid solution (50% concentration) of 0.1% oil, kept vacuum stirring 15 minutes down at 90 ℃, subsequently the light phase of centrifuging and taking;
2. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
3. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters initial refining oil.
4. dry degumming: initial refining oil is used the heavy citric acid solution (50% concentration) of 0.1% oil, kept vacuum stirring 15 minutes down at 90 ℃, subsequently the light phase of centrifuging and taking;
5. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 0.5% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
6. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 220 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters double refining oil.
Process appearance and product quality are as shown in the table:
Embodiment 6
Ester exchange
Adopt the used crude oil of Test Example 1;
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), 18% mass concentration sodium hydroxide solution, the sodium methoxide powder,
Pure water is made by counter-infiltration R/O film;
Technological process is following:
Getting 700g hair palm oil operates as follows:
1. dry degumming: in oil sample, add the heavy citric acid solution (50% mass concentration) of 0.01% oil.Kept vacuum reaction 15 minutes down at 90 ℃, the light phase of centrifuging and taking;
2. alkali refining: in 90 ℃ of reactions 30 minutes down, the light phase of centrifuging and taking; Add alkali number=7.13 * 10
-4* M
Oil* AV * (1+ excess alkali quantity), excess alkali quantity is 20%, alkali lye amount=add alkali number/0.18 promptly adds the 20.13g sodium hydroxide solution
3. remove soap: 90 ℃ with the heavy deionized water and stirring of 20% oil 10 minutes, deionized water need be preheated to 85 ℃;
4. dry: as under 90 ℃ and vacuum, to keep stirring 1 hour;
5. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
6. chemical ester exchange: bleached oil is warming up to 90 ℃, adds the heavy sodium methoxide of 0.1% oil, reaction is after 30 minutes under vacuum; Use 15% mass concentration; The heavy citric acid solution cessation reaction of 1.7% oil is neutral until pH value with the hot water washing more than 3 times subsequently, centrifugalize oil phase;
7. dry: stirred 30 minutes after oil phase is warming up to 90 ℃, during keep vacuum;
8. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 240 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are following:
Embodiment 7
Glue+the ester exchange of acidifying water wash-out
Adopt the used crude oil of Test Example 1;
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), 18% mass concentration sodium hydroxide solution, the sodium methoxide powder,
Pure water is made by counter-infiltration R/O film;
Technological process is following:
Getting 700g hair palm oil operates as follows:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.1% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. alkali refining: in 90 ℃ of reactions 30 minutes down, the light phase of centrifuging and taking; Add alkali number=7.13 * 10
-4* M
Oil* AV * (1+ excess alkali quantity), excess alkali quantity is 20%, alkali lye amount=add alkali number/0.18 promptly adds the 20.13g sodium hydroxide solution
3. remove soap: 90 ℃ with the heavy deionized water and stirring of 20% oil 10 minutes, deionized water need be preheated to 85 ℃;
4. dry: as under 90 ℃ and vacuum, to keep stirring 1 hour;
5. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
6. chemical ester exchange: bleached oil is warming up to 90 ℃, adds the heavy sodium methoxide of 0.1% oil, reaction is after 30 minutes under vacuum; Use 15% mass concentration; The heavy citric acid solution cessation reaction of 1.7% oil is neutral until pH value with the hot water washing more than 3 times subsequently, centrifugalize oil phase;
7. dry: stirred 30 minutes after oil phase is warming up to 90 ℃, during keep vacuum;
8. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 240 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and product quality are following:
Embodiment 8
The washing refined oil
The refined oil quality is as shown in the table:
Pure water is made by counter-infiltration R/O film;
Technological process is following:
Getting 400g refining palm oil operates according to the following steps
1. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes;
2. separate: under the 4500rpm centrifugal 15 minutes, get light phase;
3. dry: stirred 30 minutes after being warming up to 90 ℃, during keep vacuum;
Product quality is as shown in the table:
This embodiment proves and washes the content that refined oil can be controlled 3-MCPD in the grease equally.
Embodiment 9
Acidifying water wash-out glue+alkali refining+washing
The crude oil quality is seen table 1
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 800g hair palm oil operates according to the following steps:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.1% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. alkali refining: in 90 ℃ of reactions 30 minutes down, the light phase of centrifuging and taking; Add alkali number=7.13 * 10
-4* M
Oil* AV * (1+ excess alkali quantity), excess alkali quantity is 20%, alkali lye amount=add alkali number/0.18 promptly adds the 22.74g sodium hydroxide solution
4. remove soap: 90 ℃ with the heavy deionized water and stirring of 20% oil 10 minutes, deionized water need be preheated to 85 ℃;
5. dry: as under 90 ℃ and vacuum, to keep stirring 1 hour;
6. decolouring: under 110 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
7. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
8. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
9. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 240 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Process appearance and quality are as shown in the table:
Embodiment 10
Dry degumming+washing+decolouring
Adopt the used crude oil of Test Example 1
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 600g hair palm oil operates according to the following steps:
1. dry degumming: the hair palm oil is used the heavy citric acid solution (50% concentration) of 0.1% oil, kept vacuum stirring 15 minutes down at 90 ℃, subsequently the light phase of centrifuging and taking;
2. washing: 90 ℃ with the heavy deionized water and stirring of 20% oil 10 minutes, deionized water need be preheated to 85 ℃;
3. dry: as under 90 ℃ and vacuum, to keep stirring 1 hour;
4. decolouring: under 90 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
Process appearance and quality such as following table are said:
Embodiment 11
Decolouring+deodorization VS decolouring+washing+deodorization
Adopt raw material such as Test Example 1:
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
1. decolouring: under 110 ℃,, kept vacuum stirring 30 minutes to adding the heavy Taiko Supreme of 1% oil 1B in the crude oil; Cross and filter bleached oil;
2. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
3. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
4. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 260 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
Both qualities are as shown in the table:
Embodiment 12
Crude oil → (washing) → deodorization
Adopt raw material with Test Example 1
1. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. deodorization: to feeding nitrogen (serve as and stir and the deodorization medium) in the oil, vacuum is approximately 10-20mBarA, after keeping 1 hour under 240 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
(wherein step 1 is implemented in an experiment with 2)
Process appearance and product result are following:
Embodiment 13
The applicability of other greases
Raw material: the corn oil quality is as shown in the table:
Atlapulgite: Taiko Supreme 1B (H
2SO
4Activation), pure water is made by counter-infiltration R/O film
Technological process is following:
Getting 800g hair corn oil operates according to the following steps:
1. acidifying water wash-out glue: the deionized water that uses heavy citric acid solution (50% mass concentration) of 0.5% oil and 10% oil to weigh; Centrifugation (4500rpm after stirring 30 minutes under 80 ℃; 15 minutes) get light phase, this step carries out twice, gently promptly oily mutually next step refining flow process that gets into;
2. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
3. alkali refining: in 90 ℃ of reactions 30 minutes down, the light phase of centrifuging and taking; Add alkali number=7.13 * 10
-4* M
Oil* AV * (1+ excess alkali quantity), excess alkali quantity is 20%, alkali lye amount=add alkali number/0.18 promptly adds the 18.25g sodium hydroxide solution
4. remove soap: 90 ℃ with the heavy deionized water and stirring of 20% oil 10 minutes, deionized water need be preheated to 85 ℃;
5. dry: as under 90 ℃ and vacuum, to keep stirring 1 hour;
6. decolouring: under 110 ℃, dried oil plant is added the heavy Taiko Supreme of 1% oil 1B, kept vacuum stirring 30 minutes; Cross and filter bleached oil;
7. washing: bleached oil adds the heavy deionized water (being preheated to more than 80 ℃) of 20% oil down at 85 ℃ and stirred 10 minutes, and light phase is got in centrifugation subsequently;
8. dry: stirred 30 minutes after gently being warming up to 90 ℃ mutually, during keep vacuum;
9. deodorization: bleached oil is fed nitrogen (serve as and stir and the deodorization medium), and vacuum is approximately 10-20mBarA, after keeping 1 hour under 240 ℃, sheds heating jacket, is abolishing vacuum below 50 ℃ and is stopping nitrogen, crosses and filters refined oil.
(wherein step 7 is implemented in an experiment with 8)
Process appearance and product are as shown in the table:
The above is merely preferred embodiment of the present invention; Be not in order to limit essence technology contents scope of the present invention; Essence technology contents of the present invention is broadly to be defined in the claim scope of application, and if any technological entity or method that other people accomplish are defined identical with the claim scope of application; Also or a kind of change of equivalence, all will be regarded as and be covered by among this claim scope.
Claims (17)
1. in the process of polished fat, control 3-chloro-1 for one kind, the method for 2-propane diols or its ester content, the process of described polished fat comprise (D) decolouring step; (G) deodorization step; It is characterized in that described method comprises:
Between described decolouring step (D) and deodorization step (G), carry out the following step: (E) bleached oil is carried out the step that contacts with water, this step comprises mixes (E1) with water; And/or (E2) step of transesterification; (F) water phase separated, the oil phase of drying steps (E) gained.
2. the method for claim 1 is characterized in that, in the said step (E), the consumption of said water is more than or equal to the heavy 0.5wt%. of the bleached oil of step (D) gained
3. the method for claim 1; It is characterized in that; Described step of transesterification (E2) comprising: the bleached oil of step (D) gained is warming up to 90 ℃-120 ℃, adds the catalyst that accounts for said bleached oil weight 0.1-2wt%, preferably under vacuum, react after 30 minutes; Cessation reaction is washed to pH value and is neutral;
Described catalyst is selected from the mixture of sodium methoxide, NaOH and glycerine or the mixture of alkali metal and glycerine; Perhaps
Described step of transesterification (E2) comprises that the bleached oil with step (D) gained is warming up to 40-60 ℃, adds the ester exchange enzyme that accounts for said bleached oil weight 0.1-2wt%, preferably under vacuum, reacts after 30 minutes cessation reaction.
4. the method for claim 1 is characterized in that, the step (A) of before the decolouring step, coming unstuck.
5. method as claimed in claim 4 is characterized in that, the described step of coming unstuck comprises crude oil, come unstuck medium and water mixed method; The described medium that comes unstuck is selected from citric acid solution, phosphoric acid solution or degummase; The described medium that comes unstuck is the 0.05wt% that is not less than crude oil weight, and the water yield is not less than the 0.5wt% of crude oil weight; The described medium that comes unstuck is in the gross weight of solution, and wherein the concentration of acid is not less than 5wt%;
Preferably, reaction system was carried out under the PH-5-6 2-4 hour at 50-80 ℃.
6. like the described method of claim 1-6; It is characterized in that; Between the described step of coming unstuck (A) and described (D) decolouring step, have (B) alkali refining step and (C) remove the soap step; Described alkali refining step (B) comprises in the oil phase of step (A) gained and adds aqueous slkali, with the oil phase of neutralization procedure (A) gained; The described soap step (C) of removing comprises that adding hot water is to remove soap stock in the oil phase of step (B) gained.
7. method as claimed in claim 6 is characterized in that,
Described decolouring step (D) comprising:
(i) under the vacuum oil phase of step (C) gained is warming up to 80-90 ℃;
(ii) add the sulfuric acid treated earth;
(iii) be warming up to 100-110 ℃ again, keep vacuum stirring to be not less than 10 minutes; With
(iv) filter to remove described sulfuric acid treated earth.
8. a control grease forms 3-chloro-1 in the deodorization step; The method of 2-propane diols or its ester comprises: before the deodorization step, the refined oil of decolouring is carried out the step (E) that contacts with water; This step comprises the step (E1) that adds the water mixing, and/or step of transesterification (E2); And, water phase separated, the step of the oil phase of dry gained (F).
9. method as claimed in claim 8 is characterized in that its phosphorus content is lower than 5ppm behind the grease-decolor; Preferably, less than 3ppm; More preferably, less than 1ppm.
10. method as claimed in claim 8; It is characterized in that; Described step of transesterification (E2) comprising: the refined oil of described decolouring is warming up to 90 ℃-120 ℃, adds the catalyst that accounts for said bleached oil weight 0.1-2wt%, preferably under vacuum, react after 30 minutes; Cessation reaction is washed to pH value and is neutral;
Described catalyst is selected from the mixture of sodium methoxide, NaOH and glycerine or the mixture of alkali metal and glycerine; Perhaps
Described step of transesterification (E2) comprises that the refined oil with described decolouring is warming up to 40-60 ℃, adds the ester exchange enzyme of the refined oil weight 0.1-2wt% that accounts for said decolouring, preferably under vacuum, reacts after 30 minutes cessation reaction;
11. method as claimed in claim 8 is characterized in that, in the said step (E), the consumption of said water is more than or equal to the heavy 0.5wt% of the refined oil of said decolouring; Said be blended in not to be higher than under 95 ℃ carry out.
12. the method for a polished fat is characterized in that, described method comprises the following steps:
(A) step of coming unstuck;
(D) to the processing of decolouring of the oil phase of step (A) gained;
(E) bleached oil of step (D) gained is carried out the step that contacts with water, this step comprises:
(E1) and water mix; And/or
(E2) step of transesterification;
(F) water phase separated, the resulting oil phase of drying steps (F); With
(G) oil phase to step (F) gained feeds nitrogen or steam, makes its deodorization.
13. method as claimed in claim 12 is characterized in that,
Also comprise (B) alkali refining step in step (A) with (D): the oil phase that adds alkaline solution neutralization procedure (A) gained;
(C) remove the soap step: in the oil phase of step (B) gained, add hot water to remove soap stock;
(C-1) water phase separated, dry gained oil phase step: the oil phase that step (C) is obtained carries out drying;
Described step of transesterification (E2) comprising: the bleached oil of step (D) gained is warming up to 90 ℃-120 ℃, adds the catalyst account for said bleached oil weight 0.1-2wt%, and preferably reaction after 30 minutes under vacuum, cessation reaction is washed to pH value and is neutral;
Described catalyst is selected from the mixture of sodium methoxide, NaOH and glycerine or the mixture of alkali metal and glycerine; Perhaps
Described step of transesterification (E2) comprises that the bleached oil with step (D) gained is warming up to 40-60 ℃, adds the ester exchange enzyme that accounts for said bleached oil weight 0.1-2wt%, preferably under vacuum, reacts after 30 minutes cessation reaction;
The described step of coming unstuck comprises crude oil, the methods such as medium and water mixing of coming unstuck; The described medium that comes unstuck is selected from citric acid solution, phosphoric acid solution or degummase; The described medium that comes unstuck is the 0.05wt% that is not less than crude oil weight, and the water yield is not less than the 0.5wt% of crude oil weight; The described medium that comes unstuck is in the gross weight of solution, and wherein the concentration of acid is not less than 5wt%;
Preferably, the reaction system of the said step of coming unstuck was carried out under the PH-5-6 2-4 hour at 50-80 ℃.
14. method as claimed in claim 13 is characterized in that,
Described decolouring step (D) comprising:
(i) under the vacuum oil phase of step (C-1) gained is warming up to 80-90 ℃;
(ii) add the sulfuric acid treated earth;
(iii) be warming up to 100-110 ℃ again, keep vacuum stirring to be not less than 10 minutes; With
(iv) filter to remove described sulfuric acid treated earth;
In the said step (E), the consumption of said water is more than or equal to the heavy 0.5wt% of the bleached oil of step (D) gained; Said be blended in not to be higher than under 95 ℃ carry out.
15., it is characterized in that like the arbitrary described method of claim 1-14, after described method also is included in the deodorization step, make refined oil carry out water-washing step (E) again, this step comprises the step (E1) that adds the water mixing, and/or step of transesterification (E2); And, the step of the step (F) of the moisture oil phase of dry gained.
16. like the arbitrary described method of claim 1-14; It is characterized in that described crude oil or described bleached oil are selected from soybean oil, rapeseed oil, sunflower oil, coconut oil, peanut oil, safflower seed oil, cottonseed oil, rice bran oil, corn oil, olive oil, hydrogenated oil and fat, palm oil vegetable fat and animal fat or its mixture.
17. the refined oil according to the arbitrary said method of claim 1-16 obtains is characterized in that in the gross weight of said refined oil, wherein the 3-chloro-1, the content of 2-propane diols and/or its ester is smaller or equal to 0.5ppm.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010228009.XA CN102334563B (en) | 2010-07-16 | 2010-07-16 | Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil |
| ES11806292T ES2613987T5 (en) | 2010-07-16 | 2011-07-13 | Control procedure for the level of 3-chloro-1,2-propanediol or their esters in oils and fats |
| EP11806292.6A EP2594625B2 (en) | 2010-07-16 | 2011-07-13 | Method of controlling level of 3-chloro-1,2-propanediol or esters thereof in oils and fats |
| MYPI2013000130A MY161245A (en) | 2010-07-16 | 2011-07-13 | Method of controlling the amount of 3-chloro-1, 2-propanediol or ester thereof in fats and oils |
| PCT/CN2011/077096 WO2012006950A1 (en) | 2010-07-16 | 2011-07-13 | Method of controlling level of 3-chloro-1,2-propanediol or esters thereof in oils and fats |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010228009.XA CN102334563B (en) | 2010-07-16 | 2010-07-16 | Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102334563A true CN102334563A (en) | 2012-02-01 |
| CN102334563B CN102334563B (en) | 2015-03-25 |
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|---|---|---|---|
| CN201010228009.XA Active CN102334563B (en) | 2010-07-16 | 2010-07-16 | Method for controlling content of 3-chloro-1,2-propanediol or ester thereof in oil |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP2594625B2 (en) |
| CN (1) | CN102334563B (en) |
| ES (1) | ES2613987T5 (en) |
| MY (1) | MY161245A (en) |
| WO (1) | WO2012006950A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102504950A (en) * | 2011-11-08 | 2012-06-20 | 安徽绿健生物科技有限公司 | Method for decolorizing tea seed oil |
| CN103261386A (en) * | 2010-11-19 | 2013-08-21 | 荷兰洛德斯克罗科兰有限公司 | Method for producing refined vegetable oil |
| CN103525548A (en) * | 2013-11-06 | 2014-01-22 | 江南大学 | Degumming method for reducing content of chlorine sources and 3-monochlorpropane-1,2-diol ester precusor substances in vegetable oil |
| CN104531349A (en) * | 2015-01-23 | 2015-04-22 | 上海交通大学 | Method for reducing 3-chlorine-1,2-propylene glycol ester during grease processing |
| CN104698113A (en) * | 2013-12-06 | 2015-06-10 | 上海良友（集团）有限公司 | A method of detecting 3-chloro-1,2-propanediol fatty acid ester and epoxy glycerin fatty acid ester in edible fat and oil |
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| USRE48861E1 (en) | 2010-09-03 | 2021-12-28 | Stepan Specialty Products, Llc | Elimination of organohalo and oxirane species in carboxylic acid ester streams |
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| CN113122382B (en) * | 2019-12-31 | 2024-02-20 | 丰益(上海)生物技术研发中心有限公司 | Preparation method of grease with low pollutant content |
| CN111349513A (en) * | 2020-03-12 | 2020-06-30 | 青岛天祥食品集团有限公司 | Processing technology for controlling generation of 3-MCPD ester and glycidyl ester in edible oil |
| CN113755240A (en) * | 2021-09-17 | 2021-12-07 | 中粮农业产业管理服务有限公司 | Method for removing trichloropropanol ester and glycidyl ester in palm oil |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2594625A1 (en) | 2013-05-22 |
| CN102334563B (en) | 2015-03-25 |
| EP2594625B2 (en) | 2019-12-04 |
| EP2594625B1 (en) | 2016-11-16 |
| EP2594625A4 (en) | 2014-09-10 |
| MY161245A (en) | 2017-04-14 |
| WO2012006950A1 (en) | 2012-01-19 |
| ES2613987T5 (en) | 2020-08-07 |
| ES2613987T3 (en) | 2017-05-29 |
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Application publication date: 20120201 Assignee: Yihai Jiali Food Technology Co.,Ltd. Assignor: WILMAR (SHANGHAI) BIOTECHNOLOGY RESEARCH & DEVELOPMENT CENTER Co.,Ltd. Contract record no.: X2023310000046 Denomination of invention: Method for controlling the content of 3-chloro-1,2-propanediol or its esters in fats and oils Granted publication date: 20150325 License type: Common License Record date: 20230410 |